E filament blended therewith aqueous transfer of dye from water soluble filament to water insolubl

ABSTRACT

PROCESS FOR EFFECTING RANDOMLY DISTRIBUTED COLORATION OF TEXTILE MATERIALS IS PROVIDED COMPRISING APPLYING TO TEXTILE MATERIALS AT LEAST ONE WATER-SOLUBLE COLORING MATERIAL COMPRISING A WATER-SOLUBLE POLYMER CONTAINING A COLORANT WHICH EXHIBITS GREATER AFFINITY FOR THE TEXTILE MATERIAL THAN FOR SAID POLYMER AND IS CAPABLE OF COLORING SAID TEXTILE MATERIAL; HEATING THE RESULTING TEXTILE MATERIAL WHILE IN WET STATE TO EFFECT MIGRATION OF THE COLORANT FROM THE WATER-SOLUBLE COLORING MATERIAL TO THE TEXTILE MATERIAL WITH RESULTANT RANDOM COLORATION OF SAID TEXTILE MATERIAL, AND THEREAFTER REMOVING THE WATER SOLUBLE PORTION OF SAID COLORING MATERIAL FROM THE TEXTILE MATERIAL.

United States Patent US. Cl. 8-14 16 Claims ABSTRACT OF THE DISCLOSUREProcess for effecting randomly distributed coloration of textilematerials is provided comprising applying to textile materials at leastone water-soluble coloring ma terial comprising a water-soluble polymercontaining a colorant which exhibits greater affinity for the textilematerial than for said polymer and is capable of coloring said textilematerial; heating the resulting textile material while in a wet state toeffect migration of the colorant from the water-soluble coloringmaterial to the textile material with resultant random coloration ofsaid textile material, and thereafter removing the water soluble portionof said coloring material from the textile material.

This invention relates to processes for making textile materialsexhibiting a randomly distributed coloration. More particularly, theinvention relates to processes for making randomly colored textilematerials comprising applying water-soluble coloring materialscontaining a colorant, for example, a dye or pigment, to the textilematerials and effecting migration of the colorant from the water-solublematerials to the textile materials by heating the treated textilematerial while in a wet state.

Many methods have been heretofore employed to obtain randomlydistributed coloration of textile materials. As employed herein, thephrase randomly distributed coloration of textile materials is intendedto encompass textile materials exhibiting a speckled, mottled orsprinkled coloration generally, although not necessarily, involvingmultiple colors. In all instances, however, the coloration is randomlydistributed throughout the textile material. For example, textilematerials in the form of yarns or fabrics have been manufactured byblending or doubling at least two differently colored fibers. However,the color tone of the resulting textile materials has been found toundergo undesirable changes when said textile materials are rubbed andone of the colored fibers comprising the textile materials falls out.The problem is most acute when natural fibers and synthetic fibers aredifferently colored and are blended. The undesirable change in colortone is quite apt to Occur because the colored natural fibers fall outeasily. Also, it is difficult to obtain randomly distributed colorationof textile materials having a desired color tone, especially amulticolor effect, by simply blending or doubling differently coloredfibers or yarns. Generally, complicated control of blending or doublingis required. Furthermore, such complicated methods are commerciallyundesirable in Another method for effecting randomly distributedcoloration of textiles comprises knitting yarn into a prefabric,printing color on said fabric, unravelling the prefabric to form yarnand thereafter producing a new fabric. The fabrics obtained in saidmethod however, have undesirable color effects which are systematicallyrepeated. Also, said method requires many production steps withresultant high production cost.

Accordingly, it is an object of this invention to provide methods foreffecting randomly distributed coloration of textiles with deep andsharp color definition. Another object of this invention is to providemethods for effecting random coloration of textile materials, forexample, yarns, woven fabrics or non-woven fabrics.

Still another object of the invention is to provide methods foreffecting random coloration of textiles with a multi-color effect.

Yet another object of the invention is to provide an improved method ofrandom coloration which comprises applying a water-soluble coloringmaterial containing a colorant to a textile material and migrating thecolorant from the water-soluble material to the textile material.

A further object of the invention is to provide an improved method ofrandom multiple coloration, in which each colorant is easily applied totextiles and the color effect is easily controlled.

These as Well as other objects are accomplished by the present inventionwhich provides a process for effecting randomly distributed colorationof textile materials comprising applying to textile materials at leastone water soluble coloring material comprising a water soluble polymercontaining a colorant which exhibits greater affinity for the textilematerial than for said polymer and is capable of coloring said textilematerial; heating the resulting textile material while in a wet state toeffect migration of the colorant from the water soluble coloringmaterial to the textile material with the resultant random coloration ofsaid textile material, and thereafter removing the water soluble portionof said coloring material from the textile material.

It has been found in the present invention that the colorant included inthe water-soluble material is capable of migrating from thewater-soluble material to the waterinsoluble textile material to whichsaid water-soluble material containing the colorant, for example a dyeor pigment, is applied. Migration is effected when the treated textilematerial is heated while still in a wet state and said water-solublematerial is swelling. It has been found that said migration occurseasily when water-soluble materials, in the form of chips, scales,granules or fibrous materials are used.

Thewater-soluble coloring materials employed in the present inventionare formed from water-soluble polymers, for example, polyvinyl alcohol,polyvinyl alcohol derivatives, sodium alginate, starch, sodium salt ofcarboxymethyl cellulose, acetylized starch, hydroxyethyl cellulose,sodium salt of carboxymethyl starch and the like.

The water-soluble coloring materials can be used in the form of chips,scales, granules or fibrous materials, for example, short-cut fibers,staples, continuous filaments. Especially preferred water-solublecoloring materials are in'the form of fibrous materials.

The water-soluble coloring materials in the form of filaments can bemanufactured by conventional techniques employed for fiber making. Forexample, a preferred method comprises preparing an aqueous solution of awater-soluble polymer as an aqueous spinning solution, extruding thespinning solution into a coagulating bath or dry air, preferably hotair, through a spinning nozzle and drawing and/or heat-treating theextruded filaments, if desired.

Another method of making the water-soluble coloring materials in fibrousform comprises extruding an aqueous solution of a water-solublepolymeritthrough a slit for forming a film, coagulating, drawing and/orheat-treating and thereafter cutting, slitting or splitting the film toobtain flat tapes, scales or split fibers.

In the above-mentioned methods, the temperature at which the fibrouscoloring materials will dissolve or swell in water can be easilycontrolled by variations of the draw-ratio of the coagulated materials,the temperature of heat-treatment or the treating times.

These methods can be advantageously employed to obtain water-solublematerials exhibiting the dissolving or swelling temperatures required inthe subsequent steps of the process of the present invention. Thedissolving temperature of the water-soluble materials can be also variedin accordance with the properties of the colorants or textile materialsemployed. The water-soluble fibrous coloring materials obtained by theabove methods are advantageously applied by blending or doubling withother textile materials, for example, staple fibers, filaments, webs,slivers, tows, threads. Furthermore, these fibrous materials can be cut,if desired, to prepare the watersoluble coloring materials in the formof short-cut fibers I or powders.

In these methods, it is possible to change the form or size of thewater-soluble coloring materials by varying the form or size of theextrusion die or spinneret employed. An especially preferred polymer foruse as the water-soluble coloring material in accordance with thepresent invention is polyvinyl alcohol. Said polymer can be easilyformed into filaments or films and the dissolving temperature of theresulting materials can be easily controlled.

Furthermore, the water-soluble materials can be obtained by cutting orreducing sheets, films or blocks of the water-soluble coloringmaterials. The water-soluble coloring materials obtained in said methodcan be obtained in the form of chips, scales, granules or powders. Inthis case, since the size of the materials thus obtained is irregular,varied color effects can be obtained. However, it is not easy to controlthe state or extent of the dissolving or swelling of these water-solublematerials in water. Therefore, it is considered advantageous for thewater-soluble coloring materials to be made by the fiber or film-formingprocesses.

The colorants can be incorporated in the water-soluble materials to formthe water-soluble coloring materials by various methods. For example,the colorants can be mixed in the above-mentioned aqueous solution ofthe watersoluble polymers by either dissolving or dispersing saidcolorants therein prior to extrusion. If desired, dying auxiliaries suchas wetting or dispersing agents can also be employed.

Furthermore, the water-soluble coloring materials containing thecolorant can be obtained by applying the colorant to the water-solublematerials, for example, by coating or impregnating the fibrouswater-soluble material with a solution or dispersion of the colorant. Inthis invention, the water-soluble coloring materials which are obtainedby extruding an aqueous solution of water-soluble polymers admixed withthe colorant is especially preferred for deeply and sharply coloring thetextiles.

The colorants employed in the present invention must have an affinityfor the textile materials only; colorants having affinity for thewater-soluble polymers forming the coloring materials cannot be used. Ifthe colorant interacts in some manner with the water-soluble polymers,it is diflicult to produce said coloring materials and the colorant willnot migrate from the water-soluble materials to the textile. Therefore,for example, combinations such as the sodium salt of carboxymethylcellulose containing primary hydroxyl groups or sodium alginate andreactive dyestuffs cannot be employed.

The colorant content in the water-soluble coloring ma terial is at least3% by weight, and preferably more than 5% by weight for deep and sharpcoloring. Said colorant content is higher than the content of thecolorant generally added to the spinning solution for manufacturingdope-dyed fibers.

The water-soluble coloring materials can be applied to the textilematerials by the following methods:

One method comprises blending or doubling and twisting the fibrouscoloring materials with textile materials, for example, in the form ofstaple fibers, filaments, yarns, tows, slivers or webs. This method canbe conducted in a conventional manner, for example, mixing, spinning,doubling and twisting or wrapping. In such methods, the fibrous coloringmaterials impart an interesting coloration to textiles. For example,thermoplastic yarns blended with the fibrous coloring materials can becrimped to obtain randomly colored textured yarn by using conventionalmeans such as false-twisting. In these cases, the content of thecoloring materials in the textured yarn is preferably less than 40 wt.percent, especially 1 to 30 wt. percent, for imparting sharp colorationto the yams.

Of course, two or more of the coloring materials each having differentcolorants can be used to obtain multicoloration.

Other methods for applying the coloring materials to the textilematerials can be employed, for example, dipping the textile materialsinto a dispersion or solution of the coloring materials or spraying orcoating the textile materials with a dispersion or solution of thecoloring materials or spraying or coating the textile materials with adispersion or solution of the coloring materials.

In these instances, the coloring material is preferably in a finelydivided state, for example, scales, chips, granules, powders or shortcut fibers. These materials can be dispersed in water alone byconventional means. These coloring materials, however, must not dissolvein the water before being fixed to the textile materials. Therefore,when employing the above-mentioned method, the coloring materialsemployed must have a dissolving temperature higher than the temperatureof the water used in the dispersion. For example, when the coloringmaterials are dispersed in water at room temperature, said materialsmust have a dissolving temperature of about 40 C. to C. or higher. Underthese conditions, the water-soluble materials in the dispersion swellwithout dissolving out in the water. In this form, the dispersion isquite cohesive to textile materials and when the textile materials aretreated by the dispersion, the coloring materials can be easily fixed tothe surface of the textile materials.

Another method for applying the coloring materials to the textilematerials can be conducted by adhering the coloring materials to thesurface of the textile materials, for example, by conventional staticflocking means or by coating or printing the mixture of the coloringmaterials or the dispersion of said materials and other water-solubleadhesives onto the textile materials.

Furthermore, the water-soluble materials can be applied by blending ormixing in the webs for non-woven fabrics as the textile materials.

After the water-soluble coloring material has been applied to thetextile materialfthe resulting textile material, while in a wet state,is heated to swell the water-soluble materials and effect migration ofthe colorant from the coloring materials to the textile materials. Thisheat-treatment can be generally conducted by such conventional means asby steaming such as with raw steam, high pressure steam or superheatedsteam. When the heat-treatment is effected by steaming, the textilematerials in the form of yarns, tows, slivers and the like arepreferably treated in the form of wound layers, for example, in the formof a cheese or cone.

In an alternative method, the treated textile materials can be dampenedand thereafter heated. After application of the dispersion of thecoloring materials to the textile materials, the treated textiles can bedirectly heated Withpolymerization: 1700) and Sumikaron Red FB (C.I.Disout drying. The heat-treatment must be conducted at a perse Red 60)which was dialyzed for one day by using sufficiently high temperature tocause swelling of the parchment paper, at a weight ratio of 100:15, andtherecoloring material and migration of the colorant from the afteradding water to the mixture to obtain a weight ratio water-solublematerial to the textile materials. of Watenspinning solution of 60:40.Filaments were Effective temperatures for causing migration of theformed from said spinning solution by extruding said solucolorant andcoloring the textile commence at the least tion into hot air at 110 C.and drawing said filaments in 100 C., and preferably at at least 120 C.a ratio of 1:40 at 150 C. in a heated air zone. The size Employing theabove processes, textile materials are of the filaments obtained by theabove-described method given a deep and sharply defined random incoloration. was about 20 deniers and said filaments exhibited a dis-Upon completion of the above-described heat-treatsolving temperature of70 C.

ment, said colored textile materials are treated with an The resultingcolored filaments were employed as wateraqueous solution maintained at atemperature higher than soluble coloring materials and were doubled andtwisted the dissolving temperature of the water-soluble coloring in 70turns per meter with a textured yarn of polyester materials for removingthe water-soluble portions thereof 5 n s (U d nd up in the shape of aremaining on the surface of the textiles. It is desirable to cone. addan accelerator for dissolving the coloring mediums Thereafter, e w s edyarn Wound up in cone form in the dissolving solution, for example,organic acids, in- Was treated y means of Steaming at for 0 organicacids, bases, phenols, hydrogen peroxide or zinc Utes and pp in Water atfor a Period of chloride" minutes, whereby the polyvinyl alcoholremaining on the It is possible to apply the method of the i ti at yarnswas dissolved off. Thereafter, the textured yarns almost any point inthe overall process from the produc- Were Subjected to hYdIO-EXtIaCfiOIIand drying after tion of the initial fibers to the completed yarn orfabrics. duction and clearing treatment- In the method f the invention,it is easy to apply the The textured yarns obtained by this methodexhibited a colorant to the textile materials by using the water-solublef lf distributed color effect in red with excellent materials as acoloring medium. Whlte reslstance- The textile materials obtained inaccordance with the EXAMPLE 2 Present invention exhibit p and Sharp omlydis- Water-soluble filaments A to D containing a colorant tributedcoloration. The randomly distributed coloration were produced by usingpolyvinyl alc h l (PVA as a effect of the textile materials can beeasily changed by starting material under the conditions shown in TableI.

TABLE I Sample A B c D Starting PVA:

Degree of polymerization D Degree of saponification (percent).

ope:

PYA congfntration in aqueous spinning solution 45.0- 40.0 0

percen Col ng agent sumikaron Yellow Suminol Milling Red Sumiacryl Blue3R Sumik R FG (Cl. Disperse GW (CI. Acid (0.1. Basic Blue (Cli ispe rgeYellow 8) 0.1. 12690. Red 276). 47). Red 60) Coloring agent content toPVA (welg t p r 10 10 I S Temperature of spinning solution C 0.)- 140-135 135 I: 90,-

piunm":

Spifi n'lng temperature 0-) 100 no Spfllnlng operation D y sp sy D yspinning syst m- Dry spinning system.- Wet spinning system.

Drawing:

Draw ratio- 4. 4.. 4 4. Drawing temperature C O.) 150 150 150 8oHeat-treatment:

Temperature 0.). I 150 Treating times (seconds) 30 Property offilaments:

Deniers/filaments. 20/1 15/1 30/1 35/3 Dissolving temperature In WaterC.) 7 65 0 8o.

1 A solution of Glauber salt is used as coagulating bath.

altering the size or form of the water-soluble coloring Thereafter, eachfilament s d bl d d twisted with materials containing the colorant. yarnand further treated as shown .in Table II.

It is a major advantage of the present invention to be capable ofimparting the randomly distributed color efifect to a variety of yarnsby simple operations. TABLE II For example, randomly distributedcoloration of tex- Sample tured yarns has heretofore been unattainable,however, A B the method of the present invention makes possible the C Dobtainment of said textured yarn exhibiting randomly dis- Mixed y spunyarn tributed coloration. filament Polyacryllc of poly- Furthermore, inaccordance w1th the present method, fg; 32i? n g d s ter randomlydistributed multi-coloration of textiles is easily Textile Material set.(40" s) o g an 2 9 obtained by using two or more water-soluble coloringma- Doubling (mmS/meter) 28 28 28 terials contaimng different colorants.Steaming: o

The following examples further illustrate the present 100 100 130invention without restricting the invention to the specific (minutes) 1520 1o 30 details actually shown. Unless otherwise specified, all per- 70af f o O. 90 95 centages and parts are by weight. Treating times(minutes) 10 10 10 15 EXAMPLE 1 1 Dyed with Sumiaeryl Red ((3.1. BasicRed 18). A spinning solution was prepared by admixing polyvinyl alcohol(degree of saponification: 99.8%, degree of The results obtained areshown in Table III.

TABLE III Randomly distributed Textile materials: color combinationNylon filament yarn White and yellow. Worsted yarn White and red.Polyacrylic spun yarn Red and blue. Mixed spun yarn (polyester andcotton) White and red.

EXAMPLE 3 Three coloring materials were produced in accordance with' themethod for making sample A in Example 2, by using each of Sumikaron RedFB, Sumikaron Yellow and Sumikaron Blue GG (Anon).

The three coloring materials were respectively applied to nylon filamentyarn and colored by the same method employed in Example 2.

The resulting yarns exhibited randomly distributed coloration in acombination of red, yellow, blue and white.

EXAMPLE 4 The coloring material obtained by the method of Example 1 wastwisted in 150 turns per meter with a polyester spun yarn colored inblue by using Resolin Blue FBL (C.I. Disperse Blue 5 6). The twistedyarns were knitted into a fabric. Thereafter, said knitted fabric wastreated by means of steaming at 120 C. for 30 minutes and then wasdipped in water at 100 C. for a period of 5 minutes to remove thewater-soluble portion of the coloring materials. Thereafter, theresulting fabric was soaped, rinsed and dried.

The resulting fabric exhibited randomly distributed coloration in blueand violet and the color effect shows a shot effect.

EXAMPLE 5 Three coloring materials of the type employed in Example 3were cut in lengths of mm. and blended with polyester fibers (3 deniers,length of 38 mm.). A mixed spun yarn of said coloring materials andpolyester fiber was produced by conventional means. The yarn was treatedby means of steaming at 130 C. for 30 minutes and the water-solublepolyvinyl alcohol portion of said coloring materials were sufficientlyremoved by treatment with hot water.

The resulting spun yarn exhibited a randomly distributed multi-coloredeffect in red, blue and yellow.

EXAMPLE 6 EXAMPLE 7 Water-soluble coloring materials E and F wereproduced in filament form under the conditions shown in Table IV.

TABLE IV Dope:

Initial material Sodium alglnate. Sodium salt of carboxymethylcellulose. Initial material con- 20-.."; 60.

centration in aqueous spinning solution (percent).

TABLE IVC0ntinued Colorant and others. (021. Direct Red Supranol FastRed in water, C

Thereafter, said coloring materials were twisted with textile yarns andsaid textile yarns were randomly colored as shown in Table V.

TABLE V Coloring material E F Textile yarn Cotton spun yarn Worstedyarn. Steaming 100 0., 20 minutes 130 (3., 30 minutes. Dgssglvingtemperature, 90.

EXAMPLE 8 A film was formed by extruding an aqueous solution ofpolyvinyl alcohol containing Sumikaron Yellow into a coagulating bathcontaining Glaubers salt at 80 C. and drawing said film at a draw ratioof 5.5 at C. The resulting film had a thickness of 0.13 mm. and itsdissolving temperature was 85 C. The film was cut in lengths of 5 to 10mm. and in widths of 0.2 to 3 mm. to make the coloring materials.

Thereafter, said materials were applied to polyester spun yarn in thesame manner employed in Example 6. The resulting yarn exhibited randomlydistributed coloration.

EXAMPLE 9 Chips were produced by pulverizing a block of polyvinylalcohol containing Surnikaron Red PB. The block was formed by vacuumdrying an aqueous solution of polyvinyl alcohol. The size of the chipswas 3 mm. and their dissolving temperature was 80 C. The chips weredispersed in water containing Duck-Algin NSPL (produced by KamogawaKagaku Co., Ltd.; thickener) to form an 8% by weight dispersion of saidchips and said dispersion of coloring materials was used as a thickener.Polyester fabric was printed with said thickener. Thereafter the printedfabric was steamed at C., for 30 minutes and dipped in hot water todissolve off the polyvinyl alcohol and thickener.

The resulting fabric exhibited randomly distributed coloration on theprinted parts.

What is claimed is:

1. Process for effecting randomly distributed coloration of textilematerials comprising blending filaments of a water-insoluble textilematerial with filaments of at least one water-soluble polymer containingat least 3% by weight of a colorant which is non-reactive with the watersoluble polymer and which exhibits greater aifinity for the textilematerial than for said polymer and is capable of coloring said textilematerial, to form a yarn, heating the resulting yarn in a water wetstate to effect limited migration of the colorant from the water-solublepolymer to the textile material with resultant random coloration of saidtextile material, and thereafter removing the water soluble polymer.

2. Process as defined in claim 1 wherein said filaments ofwater-insoluble textile material and water soluble polymer are doubledtogether to form a yarn.

3. Process as defined in claim 1 wherein said filaments ofwater-insoluble textile material and water soluble polymer are twistedtogether to form a yarn.

4. Process as defined in claim 1 wherein the filaments ofwater-insoluble textile material and water soluble polymer are fibers,staples, continuous filaments or mixtures thereof.

5. Process as defined in claim 4 wherein the filaments of waterinsoluble textile material and water soluble polymer are woven togetherinto a web.

0. Process as defined in claim 4 wherein the filaments of waterinsoluble material and water soluble polymer are carded together into asilver.

7. Process as defined in claim 1 wherein the filaments of water-solublecoloring materials are doubled and twisted yarns.

8. Process as defined in claim 1 wherein the watersoluble coloringmaterials are doubled and twisted with crimped yarns.

9. Process as defined in claim 1 wherein the watersoluble coloringmaterial is doubled with a textile yarn and the resultant doubled yarnis crimped.

10. Process as defined in claim 1 wherein the water soluble coloringmaterial comprises polyvinyl alcohol and a colorant.

11. Process as defined in claim 1 wherein fibrous watersoluble coloringmaterials are blended with staple fibers and the resultant blended fiberproduct is steamed and thereafter the water-soluble materials areremoved from the colored fiber product.

1.2. Process as defined in claim 1 wherein the resulting textilematerial contains less than 40 weight percent of the water-solublecoloring material.

13. Process as defined in claim 1 wherein at least two water-solublecoloring materials, each containing a difierent colorant, are employed.

14. Process as defined in claim 1 wherein the watersoluble coloringmaterials exhibit a dissolving temperature in water of from C. to C.

15. Process as defined in claim 1 wherein the resulting textile materialis heated in the wet state at temperatures of at least C.

16. Process as defined in claim. 1 wherein the colored textile materialsare treated with an aqueous solution maintained at a temperature higherthan the dissolving temperature of the water-soluble coloring materialsthereby effecting the removal of the water-soluble portions thereofremaining on the surface of the textile.

References Cited UNITED STATES PATENTS 1,955,582 4/1934 Golding 28-76 T1,710,516 4/ 1929 Shapiro 8-14 X 3,454,347 7/1969 Leimbacher 96-1 RFOREIGN PATENTS 525,038 8/ 1940 Great Britain 8--114.6

8,309 1899 Great Britain 8--79 OTHER REFERENCES Morrell, AmericanDyestutf Reporter, Oct. 11, 1965,

30 pp. 859-862, TP890 A512.

DONALD IEVY, Primary Examiner 'U.S. Cl. XR.

829; 57-164; 28-76T, 75 WT UNITED STATES'PATENT OFFICE I .CERTIFICATE OFCORRECTION Patent 3 756, 770 Dated September 4, 1973 lnvent fl l SeiichiKobavashi et a1 It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

In the Specification:

Column 4, lines 31 and 32, delete "or spraying or coating the textilematerials with a dispersion or solution of the coloring materials",(second occurrence) Column 6, Table 11 column B, "40'5" should be -48'S.

In the Claims:

Claim 6, line 3, silver" should be sliver.

Signed and sealed this 13th day of Auglist 1974.

(SEAL) Attest:

MCCOY M. GIBSON, JR. 0. MARSHALL DANN Attesting Officer Commissioner ofPatents

